Method of applying germicidal mercurated allyl-s-triazines to textiles, optionally craeaseproofing, and textile products thereof



United States Patent METHOD OF APPLYING GERMTCIDAL MERCU- RATEDALLYlL-s-TRIAZINES T0 TEXTILES, 0P- TIONALLY CREASEPRODFING, AND TEXTILEPRGDUCTS THEREOF John Thomas Shaw, Middlesex, Frank John Gross,Mountainside, and Richard Keith Madison, Murray Hill, N..l., assignorsto American Cyanamid Company, New York, N.Y., a corporation of Maine NoDrawing. Original application Jan. 18, 1961, Ser. No. 83,368, now PatentNo. 3,130,193, dated Apr. 21, 1%4. Divided and this application Apr. 30,1963, Ser. No.

5 Claims. ((31. 8-116.3)

This application is a divisional application of Serial No. 83,368, filedJanuary 18, 1961, and now US. Patent No. 3,130,193.

This invention relates to novel germicidal or bactericidal compounds, totheir use on textile materials as durable germicidal finishes, toprocesses for applying such compounds as finishes to textile materialsand to the textile materials so treated.

More particularly, this invention relates to novel mercuratedallyltriazines as germicidal or bactericidal compounds, to their use ontextile materials as durable germicidal finishes, to the processes ofapplying said compounds as finishes to textile materials, and to thematerials so treated.

An object of the present invention is to provide a novel class ofmercurial allyltriazines, their formaldehyde condensates, and theiralkylated methylol derivatives.

A further object of this invention is to provide a durable antibacterialfinish for textile materials and in particular a finish which is durableto laundering in the presence of soaps and/or chlorine, such as isnormally employed as chlorine bleach.

A further object of this invention is to provide an antibacterial orgermicidal finish which is also capable of contributing dimensionalstability and wrinkle resistance to cellulosic materials.

A further object is to provide an antibacterial finishing compositionwhich is compatible with known textile finishing agents or resins, whichresins contribute dimensional stability and wrinkle resistance tocellulosic substrates.

A still further object of this invention is to provide a water solubleor water dispersible antibacterial finish which can be applied bystandard textile finishing methods, i.e., those normally employed by thetextile finishing industry to impart, in addition to a bactericidalfinish, Wrinkle resistance and shrinkage control to the cellulosictextile material.

These and other objects and advantages of the present invention willbecome more apparent from the detailed description thereof set forthhereinbelow.

According to the present invention, novel mercurial derivatives ofamino-s-triazines are prepared of the formula:

R is hydrogen, alkyl, (--CH ),,CH=CH or CH OR where n is a value of from1 to 3, inclusive; R -R is hydrogen, CH OR alkyl or phenyl; R R and Rare hydrogen or lower alkyl; and X is a monovalent electronegativecomponent or anionic radical such as CH COO, Cl, etc.

These compounds may be preformed and then applied to the textilesubstrates or materials or they may be formed in situ 011 suchmaterials. The mercurial compounds are derivatives of allyl substitutedamino-s-triazines with the allyl group attached to a nitrogen or to anoxygen atom which is attached to a ring carbon.

In general, these mercurated alkyl substituted aminos-triazines areprepared by reacting an appropriate allyl substituted amino-s-triazinewith mercuric acetate or a similar mercuric salt in an alcohol or watermedium acidified with a weak acid such as acetic acid. The reactionmixture is then stirred while being heated until the reaction iscompleted.

In an alternative procedure, the allyl derivative of an amino-s-triazineis first applied to the textile material and the material subsequentlytreated With a hot alcoholic solution of mercuric acetate or similarsalt, acidified with a weak acid such as acetic acid.

The values of A, R -R R and R in the general formulas will depend on thesubstitutents in the corresponding positions of the starting compounds.However, the value for R is determined by the solvent medium in whichthe reaction is carried out. If the medium is an alcohol, R will be thealkyl radical of that alcohol. When the medium is water, R will behydrogen.

The value of X, the anionic radical, will depend on the anion associatedwith mercury, of the salt used. If mercuric acetate is employed, theanion will be acetate.

If mercuric propionate is employed, the anion will be' propionate.However, X may be changed to another electronegative component byreacting the original reaction product, such as the acetate, with a saltsuch as sodium chloride or silver nitrate, whereby the acetate will beconverted to a new salt such as the chloride or nitrate.

In general, the allyl substituted amino-s-triazines employed as startingmaterials in the preparation of the compounds of this invention are wellknown and may be readily prepared. The following are illustrative of theallyl aminos-triazines which may be employed in the present invention:N-allyl substituted melamines such as N-allylmelamine,N,N-diallylmelarnine, N-allyl-N'-methylmelamine,N-allyl-N-ethylmelamine, N-allyl-N-ethylmelamine,N,N-diallyl-N-n-butylmelamine, N-allyl-N- methyl N n propylmelamine,N-allyl-N,N'-dimethylmelamine; N allyl N-phenylmelamine, N,N-diallyl-N'-phenylmelamine, and the 2,4 diamino 6 allyloxy-s-tri azines, such as 2allyloxy 4-amino-6-methylamino-s-triazine, 2 allyloxy 4-ethylamino-6methylamino-s-triazine and 2-allyloXy-4-amin0-6-phenylamino-s-triazine,and the like. It will be apparent that corresponding alkyl substitudedallyl derivatives, such as methallyl derivatives, for

The mercuric salts employable are preferably salts of aliphatic organicacids such as formic acid, acetic acid, propionic acid, butyric acid andthe like.

The solvent medium in which the mercurated allyl-striazines of thisinvention are employed is preferably an alcohol such as methanol,ethanol, propanol, butanol or the like. However, water and alcohol-watersolutions may be employed.

Whether the mercurating medium is alcoholic, aqueous or a mixture, themedium is acidified with a weak, preferably organic acid, such as aceticacid, propionic acid,

butyric acid, and the like in order to facilitate the mercuration andprevent hydrolysis of the mercury salt.

While the allylamino-s-triazines of this invention may be mercuratedprior to methylolation and alkylation if the latter is carried out, itis greatly preferred that the mercuration be effected on methylolated oralkylated methylolated allylamino-s-triazines. Mercuration of theformaldehyde condensed amino-s-triazines as noted above is carried outon the acid side in an alcoholic or aqueous medium, normally at atemperature of from 25 to 100 C. and preferably at a temperature of from60 to 80 C. for from two to forty-eight and preferably from sixteen totwenty-four hours. The mercury compound is preferably employed in anamount equal to one equivalent per double bond of theallylamino-s-triazine. While excesses may be employed, such usuallypresents recovery problems which are undesirable. Excesses of theallylamino-s-triazine may be employed usually up to about mole percentin terms of the number of double bonds present per mole of mercurycompound.

The allylamino-s-triazines of this invention may be condensed withformaldehyde to introduce methylol groups on any of the amino-nitrogenatoms which bear a hydrogen atom. These formaldehyde condensates areprepared by reacting the allyl compound with formaldehyde, preferablyunder alkaline conditions, as for example at a pH of from about 8 to 11.In general, methylolation of the allyl amino-s-triazines of thisinvention is conducted in accordance with the procedures well known tothose skilled in the art for preparing the formaldehyde condensates ofsuch materials as melamine, urea, ethylene urea, trimethylene urea andthe like to prepare aminoplast derivatives thereof. Thus, a mole offormaldehyde for each amino-hydrogen sought to be methylolated isintroduced into a reaction vessel and under alkaline conditions thereaction mixture would normally be maintained at a temperature of frombetween C. and 80 C. until condensation is complete. Normally a slightexcess of formaldehyde is employed to insure the degree of methylolationsought. Additionally, the methylol groups may be alkylated and formedinto alkoxymethyl groups such as N-methoxymethyl by reacting a methylolcompound with a suitable alcohol under acidic conditions, normally inthe presence of a mineral acid. Suitable acids for such a condensationmay be hydrochloric, sulfuric, nitric and the like. Suitable alcoholsthat may be employed in the process of this invention would include thesaturated aliphatic monohydric alcohols and particularly thosecontaining l to 4 carbon atoms, as for example methyl, ethyl, propyl,butyl and the like.

As examples of suitable methylol or formaldehyde condensates of themercurated allylamino-s-triazines of this invention, the following areillustrative: N,N-bis(3-acetoxymercuri 2 methoxypropyl)N',N-dimethylolmelamine; N (3-acetoxymercuri-2-methoxypropyl)-N-allyl-N,N-dimethylolmelamine and the like.

As examples of the alkylated methylol derivatives of the mercuratedallylamino-s-triazines of this invention, the following areillustrative: N,N-bis(3-acetoxymercuri- Z-methoxypropyl) N,'N,Ntris(methoxymethyl)melamine; N(3-acetoxymercuri-Q-methoxypropyl)-N-allyl-N',N,N"-tris(methoxymethyl)melamine; and the like.

By formaldehyde condensates of the mercurated allylamino-s-triazines ofthis invention it is meant the formaldehyde or alkylated formaldehydecondensates thereof. As will be evident from the disclosure hereinafter,these are the materials employed to provide both a germicidal and acrease-resistant finish to cellulose textile materials. Preferably thesecompounds contain at least two methylol or alkylated methylol groups ondifferent amino-nitrogens in order to insure cross-linking, andtherefore the crease resistance and shrinkage control, in finishedcellulosic textile material.

These formaldehyde condensates have the following general formula:

N o R1\ Ifil N LA R: N

where A is selected from the group consisting of OR, and N in which R isCR3 CH2( |JCHzHgX and R is selected from the group consisting ofhydrogen, alkyl, CH -CH CH CR3 0 H2o-oH21I X and CH OR and where R R areselected from the group consisting of hydrogen, CH OR alkyl and phenyland at least two of the members R R and R on different amino-nitrogens,are CH OR where R R and R are selected from the group consisting ofhydrogen and lower alkyl, and X is an anionic radical.

The N-methylol and- N-alkoxymethyl derivatives are the preferredgermicidal finishes of this invention where maximum durability isdesired. These are particularly the preferred bactericidal finishes whenthe base textile material is of a cellulosic character, as for example,cotton, rayon and the like. Also, N-methylol and N-alkoxymethylderivatives are preferred when the combination of bactericidal activityand dimensional stability and wrinkle resistance are desired oncellulosic textile materials.

As is well known, in order to cross link between two cellulosicmolecules, which reaction is necessary to impart dimensional stabilityand wrinkle resistance to the cellulose material, it is essential thatthere be more than one and preferably at least two N-methylol orN-alkoxymethyl groups in each bactericidal molecule to obtain theseeffects. When the anti-bacterial agents contain at least one methylolgroup, they are 'belived to be fiber reactive germicides. However, theynormally will not produce a cross linking that will result in wrinkleresistance and shrinkproofing for cellulose textile materials.

The compounds of this invention are either water soluble or waterdispersible and are readily applied to textile materials from aqueousmedia by any of the well known methods for applying water solubletextile resin finishes. Thus, for example, they may be padded, sprayed,applied by immersion, dipping or any of the other well known finishingtechniques.

If desired, a thermosetting a minoplast resin, as for example, of thetype well known to the textile finishing industry to be creaseproofingresins, may be applied with the antibacterial agents, either from thesame bath or subsequently from a second treating bath or solution.

As examples of suitable thermosetting aminoplast resins contemplated bythis invention, the water soluble melamine-formaldehyde resins preparedin accordance with US. Patent Nos. 2,197,357 and 2,529,856 are fullycontemplated. Examples of such resins are tris(methoxy methyl) melamine,tris(ime-thoxymethyl) dimethylol melamine hexakis('methoxymethyl)melamine, and the like. In addition to these melamine-formaldehyderesins, the urea and thiourea-formaldehyde condensates are contemplated,as are their alkylated derivatives. Thus, for example, dimethylol urea,methylated dimethylol urea and thiourea, dirnethylol ethylene urea,dimethtylol 1,2-propylene urea and thiourea, dimethylol 1,3-propyleneurea and thiourea and other related homologous compounds arecontemplated. Additionally, the formaldehyde condensates ofdicyandiamide, biuret and the like are contemplate-d, as are the watersoluble formaldehyde condensates of thiobis amides of the type describedin US. Patent No. 2,887,408.

G-uanamine formaldehydecondensates, as for example, those described inUS. Patent No, 2,887,409, including the formaldehyde condensates ofmethoxy acetoguanamine, ethoxy acetoguanamine, tertiary butoxyacetoguanamine, and the like are contemplated.

Urons may also be employed with the compounds of this invention as, forexample, N,N=bis(methoxymethyl) uron and various other and closelyrelated compounds such as are described in US. Patent No. 2,373,135.Additionally, tetrahydro triazones such as tetrahydro-S-(,B-hydroxyethyl)-5-triazone and compounds of the type described in US.Patent No. 2,304,624 are also fully contemplated.

It has been our experience that when the antibacterial agents of thisinvention do not contain methylol groups, that greater durability of thegermicidal finish is normally obtained by applying a textile resin, asfor example, any of the water soluble potentially thermosettingaminoplast resins identified hereinabove in conjunction with thegermicidal compounds.

When the germicidal compound contains methylol groups (includingalkylated methylol groups) or when a thermosetting aminoplast textilefinishing resin is employed in conjunction with the germicidal compoundsof this invention, it is advantageous to employ a suitable acidactingcuring catalyst or accelerator such as ammonium sulfate for effectingthe cure of these aminoplasts (mercurated methylol compound andthermoseting aminoplast textile finishing resin) on the textilematerial. It will be apparent that if the mercuratedallylamino-s-triazine does not contain methylol or alkylated methylolgroups, a catalyst or curing accelerator is not required to fix it uponthe textile material, and if a thermosetting aminoplast resin is notsubsequently applied, all that is required is that the treated materialbe dried. Examples of such catalysts are free acids, acid salts,alkanolamine salts, metal salts and the like of the well known types.The concentration of catalyst employed may range from about 0.1 to about25 or higher based on the weight of resin solids, depending upon theparticular catalyst type employed. Thus, for example, from between about0.1 and about of free acids, such as phosphoric, tartaric, oxalic andthe like may be employed, while in the case of ammonium chloride amountsof from between 0.5 and about 10% are used. In the case of amine saltsincluding alkanolamine salts such as diethanolamine hydrochloride, fromabout 1 to about 10% are most useful, while with respect to salts suchas magnesium chloride, amounts of from between about 5 and 25% have beensuccessfully employed. In addition to magnesium chloride, Zinc nitrate,zinc borate, aluminum chloride and other known conventional metal saltsare normally employed in amounts corresponding to from between 5 and25%, based on the Weight of the resin solids.

After the application of the methylolated mercuratedallylamino-s-triazines, with or without the addition of a thermosettingaminoplast resin, the treated textile material is dried and subjected totemperatures normally considered to be the drying and curingtemperatures employed for drying and curing for creaseproofing resins inthe textile finishing industry. Thus, for example, the treated materialmay be subjected to temperatures of from between about '180 F. to about450 F. or higher. Generally speaking, the time of drying and/or curingoperations is inversely proportional to the temperature employed and ofcourse is influenced by whether or not separate or combined drying andcuring steps are employed. Generally, when drying and curing is carriedout in a combined operation, a time of from about 1 minute to about 10minutes may be employed at temperatures of from 450 to 250 B,respectively. When the fabric has been dried preliminary to curing,curing times of the order of about 5 minutes to about A minute at atemperature of from about 250 and 450 F., respectively, have beensuccessfully employed.

The germicidal finish of this invention may be applied to textilematerials or bases, usually in the form of fabric which may be knitted,Woven, non-woven or otherwise formed, and which may be prepared fromcellulosic or non-cellulosic fibers or mixtures of the two. Thus, thetextile material may be a formed fabric of cellulosic fibers, as forexample, cotton, linen or viscose rayon or mixtures thereof, or it maybe a textile fabric prepared from acetate rayon, nylon, the polyesterfibers and acrylic fibers, Wool, silk and the like. Additionally, thetextile material may be prepared from mixtures of these and othercellulosic and non-cellulosic fibers.

Preferably, the textile material is a cellulosic material formedprincipally from cellulosic fibers. In this regard, for purposes of thisinvention, the term cellulosic fabric shall mean to include fabricscontaining at least 50% by weight of cellulosic fibers, whether they becotton, viscose rayon, linen or the like.

The antibacterial compounds of this invention are normally applied in anamount of from between 0.0001% to 2.5% on the weight of the textilematerial. The preferable amount is from between .01% to 1% based on thedry weight of the textile material to which it is applied. Inapplications where the water soluble thermosetting aminoplast resin isemployed in conjunction with the allylamino-s-triazines of thisinvention, these resins are normally applied in amounts of from betweenabout 1 and about 25% and preferably in amounts of from 2.5 to 10% basedon the dry weight of the textile material.

In order that the present invention may be more fully understood, thefollowing examples are given primarily by way of illustration. Nospecific details or enumerations contained therein should be construedas limiting the present invention except insofar as they appear in theappended claims. All parts and percentages are by weight unlessotherwise indicated.

EXAMPLE 1 N,N-bis(3-acet0xymercuri-2-meth0xypr0pyl) melamine A hotsolution of 174.9 parts (0.55 mole) of mercuric acetate and 30 parts ofglacial acetic acid in 320 parts of methanol is added to a solutionconsisting of 51.6 parts (0.25 mole) of N,N-diallylmelamine in 450 partsof methanol at 45 C. The reaction mixture is heated at the reflux for 24hours, cooled and filtered. The filtrate is concentrated in vacuo,resulting in a thick syrup. The syrup is poured into 4000 parts ofacetone, with stirring for several hours. The resultant precipitate isfiltered off and then dried in vacuo over phosphoric anhydride.

7 The hygroscopic product obtained was 122 parts (60.6% yield); M.P. 110C. to 120 C. and had the following analysis. Calculated for C H Hg N O.H O2 C, H, Hg, 49.75; N, 10.4; 0, 13.9. Found: C, 22.1; H, 2.93; Hg,50.2; N, 9.84; O, 13.0.

EXAMPLE 2 N (3 -acetxymercuri-2 -meth0xypropyl N-allylmelamine Theprocedure of Example 2 is followed substituting 48.6 parts ofN-allyl-N-ethylmelamine for the 51.6 parts of N,N-diallylmelamine.

EXAMPLE 4 N,N-bis(3-acetoxymercuri-Z-methoxypropyl)-N'- methylmelamineThe procedure of Example 1 is followed substituting 55.1 parts ofN,N-diallyl-N'-methylmelamine for the 51.6 parts of N,N-diallylmelamine.

EXAMPLE 5 N,N-bis(3-acet0xymercuri-Z-methoxypropyl)-N- phenylmelamineNH: int 1? OCH The procedure of Example 1 is followed substituting 70.6parts of N,N-diallyl-N'-phenylmelamine for the 51.6 parts ofN,N-diallylmelamine.

EXAMPLE 6 N ,N -bis (3-acetoxymercuri-2 -ethoxy propyl melamine Theprocedure of Example 1 is followed substituting an equal amount ofethanol for the methanol.

EXAMPLE 7 Reaction product ofN,N-diallyl-N',N,N"-tris(methoxymethyl)melamine and mercuric acetate Areaction product of N,N-diallyl-N,N',N"-tris(methoxymethyl)melamine andmercuric acetate is accomplished in a three-step method.

1st step.N,N-diallyl-N',N',N"-trimethylol melamine is prepared by mixing103 parts (0.5 mole) of N,N-diallylmelamine and 202 parts (2.5 moles) of37% formalin and heating to C. and the pH adjusted to 89 by adding 20%aqueous solution of caustic soda. After maintaining the temperature at85 C. and the pH at 8-9 for 30 minutes, the resulting solution is cooledto room temperature, whereupon the liquid separates into two layers.

When cooled below 10 C., the lower layer slowly solidifies. The solidmaterial is separated by filtration and dried in vacuo at 5055 C. overphosphoric anhydride.

The product amounting to 132 parts (yield) had the following analysis.

Calculated for C H N O H O: C, 45.2; H, 7.00; N, 24.4. Found: C, 45.2;H, 6.30; N, 24.0.

2nd step.A mixture consisting of 132 parts (0.42 mole) of N,Ndiallyl-N,N',N"-trimethylolmelamine, 158 parts (4.8 moles) of methanoland 0.45 part (.0032 mole) of oxalic acid dihydrate is prepared at roomtemperature and refluxed for 45 minutes. After cooling, the solution isneutralized to pH 9.610.0 with 1 N sodium hydroxide and then filteredand distilled in vacuo.

During distillation two layers are noticed. After removing all of thesolvent, a pale yellow viscous syrup re mains. The product, N,N diallylN,N,N-tris(methoxymethyl)melamine amounting to 114 parts (yield) had thefollowing analysis.

Calculated for C H N O C, 53.2; H, 7.7; N, 24.8. Found: C, 52.2; H, 7.3;N, 24.2.

3rd step.-Mercuration of product of Step No. 2 is accomplished bypreparing two separate solutions.

Solution .16.9 parts (0.05 mole) of N,N-diallyl-N,N,N"-tris(methoxymethyl)melamine is dissolved in 91 parts of methanolat room temperature.

Solution B.34.9 parts (0.11 mole) of mercuric acetate is dissolved in 65parts of methanol and 6.08 parts by weight of glacial acetic acid at theboiling point.

Solution B (boiling) is added to solution A while stirring and thecombined solutions are refluxed for 24 hours. The resultant product (aslightly turbid solution) is cooled to room temperature, filtered anddistilled in vacuo to a syrup which is water soluble.

The yield is 35.0 parts (72%).

EXAMPLE 8 2- (3-acetoxymercuri-Z-methoxypropoxy -4,6-diamino-striazine(|)C Hr-C HC HiHgO O C CH O O H; N N

To a solution of 10 parts (0.06 mole) of 2-allyloxy-4,6-diamino-s-triazine in 162 parts of methanol at 33 C. is added (insmall portions over hour period with stirring) 19.1 parts (.06 mole) ofmercuric acetate. The resultant mixture is stirred for 24 hours andallowed to stand for 5 days. The milky product is evaporated in vacuo toa syrupy product which is stirred and saturated with 79.2 parts byWeight of acetone for 3 hours. The product is filtered and the filtercake washed with acetone and then dried over phosphoric anhydride.

9 The yield is 21.3 parts; M.P. 320 C.; hygroscopic.Analysis.--Calculated for C H HgN O C, 22.9; H,

3.21; Hg, 42.4; Found: C, 22.8; H, 2.88; Hg, 43.4; N,

EXAMPLE 9 Procedures of application, drying and washing of fabricstreated with product of Example 1 APPLICATION All applications are madefrom aqueous solutions by padding through a two roll micro-set padder.

The product of Example 1 is applied at various concentrations and byseveral difierent methods, i.e.

Method A-Product applied alone Method B--Product plus creaseproofingresins Method Product app-lied alone and topped with creaseproofingresin DRYING AND CURING The cotton fabrics treated with the product ofExample 1 are laundered in a Laundromat washer as follows and aredesigned in the tables by code, i.e.

LW=0.1% neutral soap at 140 F. LWC=0.1% neutral soap plus 0.02%available chlorine at 140 F.

The synthetic or Wool fabrics are laundered in a Najort 10 reversingwasher employing 0.1% neutral soap at 100 F. followed by rinsing anddrying.

AGAR DIFFUSION TEST METHOD Bacterial inhibition tests are made ontreated fabrics by the following method.

Discs (11.5 mm.) of the treated fabrics are placed on an agar plateinoculated with bacteria culture. After several hours of contact, thediscs are removed and the plate incubated overnight. The activity of thecompound used on the fabric discs is recorded as the diameter (in mm.)of the clear area at the site of the discs. An effective agent will showa clear area with a diameter greater than that of the disc itself (11.5mm.).

The larger the clear area, the greater is the compounds activity. Theactivity under the fabric disc is also noted Where there is no zoneoutside the area covered by the fabric. The area under the disc of thefabric is rated as follows:

Cornpletely clear area underneath disc At least clear area underneathdisc SVS-Less than 75 clear area underneath disc NNo clear area Theresults are shown in Tables I to V. The following is an explanation ofthe various treatments used in Example 12 (Tables I through V).

Table l.-Applications by Methods A and B on cotton percale at 0.0001,0.001, 0.01, 0.1 and 1% solids (O.W.F.) i.e., on the weight of thefabric.

Table II.Applications by Methods A and B on cotton percale at 0.5%solids (O.W.F.).

Table lII.-Applications by Methods A and C on cotton percale at 10%solids (O.W.F.).

Table IV.-Applications by Methods A and B on fabrics of synthetic fibersand also wool flannel at 1% solids (O.W.F.).

Table V.Applications by Method B on cotton percale at 1% solids (O.W.F.)with diglycidyl ether as a creaseproofing resin in the bath.

TABLE I.--N,N-BIS(3-ACETOXYMERCURI-Q-METHOXYPROPYL)MELAMINE ON x 80COTTONVARIATIONS OF CONCENTRATIONS Zones of Inhibition (mm.)

Percent Solids (O.W.F.) E. coli, Staph. attreus Initial 25LW 25LWGInitial 25LW 25LWC 1. 19. 4 12.0 13.2; 27.0p C, 12.0p 1. 17. 8 13. 414.5. 0. 13.6 NS VS. 0. 12. 6 S 12.1. 0. VS N N. 0. VS N 12.0. 0. N N N.0. VS N G. 0. N N N. 0. N N P-C; 12.0p C; 12.0p.

(a) 5% Solids (O.W.F.) tris(methoxymethybmelamine 3.5% ammonium sulfate(based on resin solids) in treating bath.

i TABLE II.--N,N-BIS(S-ACETOXYMERCURIgbMlET'IgigOXYPROPYL)MELAM]INE ON80 x 80 Y ZonesofInhibition (111111.)

Percent Solids.

(O.W.F.) E. coli, Staph. ameus Initial 251W 25LWC Initial 25LW 25LWC 0.519. 2 C; 12.0p- C; 12.0p 21.1; 26.5p. 12.0; 21.5p..- (12.0; 19.5p. o.5(21)---- 16.6 12.6"".-- 15.4 20.2; 27.7 13.9;22.6 17.1.

(a)5% solids (O.W.F.) tris(methoxymethybmelamine 3.5% ammonium sulfate(based on resin solids) in bath.

TABLE III.-N,N-BIS(3-ACETOXYMERCURI-2METHOXYPROPYL)MELAMINE ON 80 x 80COTTON Zones of Inhibition (mm.)

Percent Solids (O.W.F.) E. coli Staph. aureus Initial 5LW 5LWC 25LW25LWC Initial 5LW 5LWC 25LW 25LWC 19 4; 20.61).-. 13.7 13. 7 12.7 12.124.7; 29.5p. 16.3; 25.7p. 15.6; 22.0p. 14.5; 20.0p 12. 9 1 0 (a)- 15.114.1 14.0 15.7 22.8; 27.0p 18.8; 24.5p 8 18.4; 22.7 17. 3

(a) Topped with 5% solids (O.W.F.) tris(methoxymethyDmelamine plus 12%magnesium chloride (based on resin solids).

TABLE IV.N,N-BIS(3 ACEIOXYMERCURI-2-METHOXY- P(I)t(\)VP1)L)MELAMINE ONVARIOUS FABRICS (1.0% SOLIDS Zones of Inhibition (mm.)

E. coli Staph. aureus Fabric Used Initial LW Initial 25LW Spun Nylon 19.0 P-O 25.7; 329p..- C.

(21).... 17. 2 13. 7 21.6; 27.21)..- 14.9, 20.713. Spun acrylic 19. 9VS-P 24.8; 31.0p..- S-P er. (2).-.. 14. 3 13. 7.-. 14.3 14.2, 22.9p.Spun polyester 20. 1 VS-P 25.0; 31.5p.-- VS.

fiber. (a). 13.1 12. 6 13. 6 12.6; 21.5p. Tafieta F11 13. 5 S-C 22.6;26.7p.-- 0; 19.811.

Acetate. (2).... 14. 5 13.0 14. 5 12.2; 21.61) Tafieta Nylon 20. 5 VS25.6; 32.5p N-P.

Fil. (a).. 13.0 S-C 13.0 P-C; 18.7p. Rayon challis 19. 3 P-C 25.4;30.1p..- C; 32.91).

(2)..-. 17. 9 12.5 23.0; 28.11).-- 14.0; 23.61). Acrylic fiber 19. 9 C25.5; 322p... 12.0; 22.7p. (21)..-- 13.1 12. 0 13. 9 12.9; 22.91). W00114. 2 N 18.0; 24.71;)... N. (11)..-. 14. 5 N 18.0; 24.01).-. N.

(a) 5% solids (O.W.F.) tris (methoxymethyDmelamine ammonium sulfate(based on resin solids) in treating bath. All fabrics washed wool/rayonwash 0.1% soap at 100 F.

Uneven zone.

ping with, the creaseproofing resin imparts greater durability. Resultson the various synthetic fabrics also show better durability when acreaseproofing resin is used in combination with the product of Example1.

In a series of applications similar to those set forth in Example 9employing the product of Example 2, good, durable zones of inhibition toE. Coli are obtained by topping the fabric treated with the product ofExample 2 with a creaseproofing resin.

EXAMPLE 1O Methylolation of N,N-bis(3-acet0xymercuri-2-methoxypropyl)melamine Wrinkle Recovery Tensile Strength H Zones ofInhibition (mm.)

E. coli S. aureus Initial l 5LW Initial 5LW Initial 5LW BLWC Initial 5LW5LWC Treated 238 223 61 15.3 12.2 12.3 19. 9; 22. 9p 12.4 12. 1Untreated 140 110 TABLE V.N,N-BIS(3 ACETOXYMERCURI-Z-ME'IHOXY-PROPYL)MELAMINE WITH 5% SOLIDS (O.W.F.) DIGLY- The results on 80 x 80cotton percale show good durability after 25LW or 25LWC when 1% ofproduct of Example 1 is used alone. However, addition of, or top- Theseresults show good wrinkle recovery and durability of germicidalproperties.

EXAMPLE 1 1 TABLE VI-ME RCURA'IED N,N-DIALLYL-N,N,N-IRIS(METHOXYMETHYDMELAMINE WITH ZINC NI'IRATE Zones of Inhibition (mm.)Percent Tensile Obs.) Wrinkle Recovery Percent Solids (O.W.F.) Zn(NO;)(deg) 01 Compound Based on E. coli S. aureus Resin Solids Initial 5LWInitial 5LW Initial 5LW 1 5LWC 1 Initial 5LW l 5LWC I 12 181 178 20. 915. 1 15.8 25. 6 17. 9 17. 5 12 220 213 24. 2 17.4 15.0 29. 4 20.5 16.8Untreated 142 137 1 Washed in soap only.

2 Washed in soap plus a commercial sodium hypochlorite solution (.0271.available chlorine).

Treated Fabrics-Dried for 2 at 225 F., Cured 1.5 at 350 F.

Thus, at 15% solids only slight improvement in the zones of inhibitionof E. coli or Staph. aureus is obtained over the solids application.However, at 15% solids a much improved wrinkle recovery is obtained.

EXAMPLE 12 Polymethylol N,N-diallylmelamine pretreated 80 x 80 cottonpercale aftertreated with mercuric acetate A swatch of 80 x 80 cottonpercale is treated in an aqueous solution (at 5% solids O.W.F.) ofpolymethylol N,N-diallylmelamine (approximately 3.3 moles of combinedformaldehyde per mole of N,N-diallylmelamine) plus 12% (based on resinsolids) of magnesium chloride. The treated fabric is dried at 225 F. for3 minutes and cured at 350 F. for 1.5 minutes.

A portion of this fabric is then extracted with hot dimethylforma'midefor 4 hours, rinsed in Water at 140 F. and air dried.

Percent N on fabric=1.17 (equivalent to 4.2% O.W.F. of polymethylolcompound).

The wrinkle recovery was 229 (W-l-F).

A 7.5 gram sample of the above treated fabric (containing 0.00104 moleof compound durably fixed thereon) is heated at reflux with stirring ina solution of 264 parts of methyl alcohol, 1.05 parts of acetic acid ad1.33 parts (0.00416 mole) mercuric acetate for 27 hours.

The fabric is then Soxhlet extracted with methanol for 24 hours and airdried.

Percent N on fabric=1.13.

The wrinkle recovery was 212 (W-l-F).

The treated fabric is washed for 25 cycles in a Laundromat washer andthen dried.

(An untreated swatch 80 x 80 cotton is also subjected to the mercuricacetate treatment only.)

Test results are shown in Table VII.

TABLE VII.80 x 80 COTTON PERCALE PRETREATED WITH POLYMETHYLOLDIALLYLMELAMINE, THEN AFTER- TREATED WITH MERCURIC ACETATE Zones ofInhibition (mm.) Percent Hg on Treatments Washes Fabric E. colt S.aureus Fabric pretreated with polymethylol None 16. 9 21.6; 23.01).-. 13. 21 diallyl melamine, 25LW 14. 6 18. 9; 2l.3p aftertreated with 25LWCNot run mercuric acetate. Fabric treated None 12. 4 with mercuric 25LWacetate only. 25LWO-. Not run...

1 Theory on basis of nitrogen analysis=5.28% Hg It will be apparent thatthe compositions of this invention may be employed in combination withother textile finishing agents, auxiliaries and assistants, as forexample, lubricants, dyes, antistatic agents and the like insofar asthese materials do not diminish the antibacterial elfects sought to beachieved thereby.

We claim:

1. The method of applying a germicidal finish to textile materials whichcomprises applying thereto in an inert liquid medium from between0.0001% and 2.5% based on the dry weight of the textile material of amercurated allyl-s-triazine of the formula:

1 4 in which R is -o Fri-d CHzHgX and R is selected from the groupconsisting of hydrogen, lower alkyl, --CH CH=CH and and where R R areselected from the group consisting of hydrogen, CH OR lower alkyl andphenyl, R R and R are selected from the group consisting of hydrogen andlower alkyl, and X is an anionic radical which forms a salt of mercuryand thereafter heating the tex tile material at elevated temperatures.

2. The process according to claim 1 in which a thermosettingcreaseproofing resin is applied simultaneously with said mercuratedalkyl amino-s-triazine whereby the germicidal finish is more durablybound.

3. The method of applying a germicidal finish to textile materials whichcomprises applying thereto from an aqueous media between 0.0001% and2.5% based on the dry weight of the textile material of a mercuratedallyl-striazine of the formula:

3 R4 R1 N N (Ii\ 2 A R; N

where A is selected from the group consisting of CR and in which R isCR3 -0 Hi( )-CHzHgX and R is selected from the group consisting ofhydrogen, lower alkyl, CH CH=CH and -CH OR-; and where R R.; areselected from the group consisting of hydrogen, CH OR lower alkyl andphenyl, and at least two of the members R R and R on diiferent aminonitrogens, are -CH OR R R and R are selected from the group consistingof hydrogen and lower alkyl, and X is an anionic radical which forms asalt of mercury and thereafter heating the textile material to elevatedtemperatures.

4. Textile material having a germicidal finish thereon comprising amercurated allyl-amino-s-triazine having the following formula:

x t t where A is selected from the group consisting of CR and 15 inwhich R is and R is selected from the group consisting of hydrogen,lower alkyl, CH CH=CH and 1 6 where A is selected from the groupconsisting of CR and in which R is 0 I'I2C CHzHgX and R is selected fromthe group consisting of hydrogen, lower alkyl, CH CH=CH and CH2OR7 and RR are selected from the group consisting of hydrogen, CH2OR7, loweralkyl and phenyl, and at least two of the members R R and R on differentamino nitrogens, are CH OR where R R and R are selected from the groupconsisting of hydrogen and lower alkyl, and X is an anionic radicalwhich forms a salt of mercury.

No references cited.

NORMAN G. TORCHIN, Primary Examiner.

H. WOLMAN, Assistant Examiner.

1. THE METHOD OF APPLYING A GERMICIDAL FINISH TO TEXTILE MATERIALS WHICHCOMPRISES APPLYING THERETO IN AN INERT LIQUID MEDIUM FROM BETWEEN0.0001% AND 2.5% BASED ON THE DRY WEIGHT OF THE TEXTILE MATERIAL OF AMERCURATED ALLYL-S-TRIAZINE OF THE FORMULA:
 2. THE PROCESS ACCORDING TOCLAIM 1 IN WHICH A THERMOSETTING CREASEPROOFING RESIN IS APPLIEDSIMULTANEOUSLY WITH SAID MERCURATED ALKYL AMINO-S-TRIAZINE WHEREBY THEGERMICIDAL FINISH IS MORE DURABLY BOUND.
 5. CELLULOSE TEXTILE FABRICHAVING A CREASE-RESISTANT GERMICIDAL FINISH PREPARED BY APPLYING THERETOFROM AN INERT LIQUID MEDIUM, A MERCURATED ALLYL AMINO-S-TRIAZINE ANDHEAT CURING SAID TRIAZINE, SAID TRIAZINE HAVING THE FOLLOWING FORMULA: